Oxidative hair-coloring mixtures containing a conditioning agent

ABSTRACT

The intermixture of milk or beer with an oxidizing agent and an oxidative hair-dye composition provides a greatly improved haircoloring mixture which conditions damaged hair, and provides uniform coloring throughout the entire hair. While any oxidizing agent can be successfully employed in the hair-coloring mixture of this invention, in the preferred embodiment the oxidizing agent comprises a solution of a hydrogen peroxide-yielding compound in a polyhydroxy alcohol. The use of the preferred oxidizing agent increases the conditioning effect of the haircoloring mixture and also substantially reduces the annoying effects inherent in the prior art agents.

United States Patent 1191 Edman et al. Au 5, 1975 [541 OXIDATIVEHAIR-COLORING MIXTURES 3,649,159 3/1972 Cohen et a1 8/102 CONTAINING ACONDITIONING AGENT R24,373 10/1957 Eckardt et a1. 8/102 [75] Inventors:Walter W. Edman, Westport; Ralph FOREIGN PATENTS OR APPUCATlQNS n Jr-, tmf r h of 224,135 11/1924 United Kingdom 424/62 Conn, 1,347,285 11/1963France 424/62 2,013,762 10/1971 Germany 424/62 [73] Assignee: gotosInternational, Inc., Darien, 298,-9 10/1965 Netherlands 424/62 onn1 [22]Filed: Apr. 9, 1973 Primary Examiner-Albert T. Meyers AssistantExaminer-Vera C. Clarke [2]] Appl' 349483 Atlorney, Agent, or FirmMe1vinI. Stoltz Related US. Application Data [63] Continuationin-pan of SenNo. 152,404, June 11, 57 ABSTRACT I971, abandoned.

The intermixture of milk or beer with an oxidizing [52] Us. CL 8/102;8/1 8/32; agent and an oxidative hair-dye composition provides 424/70;424/359 a greatly improved hair-coloring mixture which condi- [51] lm.Cl. A61K 7 13 lions damaged h ir. an provides uniform coloring [58]Field of Search H 102 H 32; 424 70 throughout the entire hair. While anyoxidizing agent can be successfully employed in the hair'coloring mix-[56] References Cited ture of this invention, in the preferredembodiment UNITED STATES PATENTS the oxidizing agent comprises asolution of a hydrogen peroxide-yielding compound in a polyhydroxyalcohol. 2149'319 3/1939 Sous 424/62 The use of the preferred oxidizingagent increases the 3011858 12/1961 Lantzetal 8/102X 1 3'I67'478 1/1965Charle at 2 conditioning effect of the hair-coloring mixture and3'l94734 7/1965 seemuner a 8/10? also substantially reduces the annoyingeffects inher- 3,210,252 10/1965 Blanke et a1 ,1 8/102 agents 3,359,16812/1967 Brechner et a1. .1 8/102 3,582,253 6/1971 Berth et a1 8/101Chums Drawmgs OXIDATIVE HAIR-COLORING MIXTURES CONTAINING A CONDITIONINGAGENT RELATED INVENTION This application is a continuation-in-part ofour previous application, Ser. No. 152,404. tiled June I l. 1971. nowabandoned.

BACKGROUND OF THE INVENTION This invention relates to the coloring ofhair on the human head, and more particularly to hair-coloring mixturesemploying oxidizing agents and commercially available dyeing or tintingcompositions generally comprising para-benzenoid-diamines, couplers,wetting and foaming agents. viscosity controlling agents, antioxidants.ammonia. isopropyl and/or ethyl alcohol. and water. hereinafter referredto as oxidative hair-dye compositions or dye intermediate" compositions.

During the last 25 years. the polularity of hair coloring hascontinually increased to afford both men and women the opportunity tomaintain a youthful appearance by coloring their graying hair. Oxidativepermanent dye mixtures have been employed to color hair regardless ofthe percentage of gray hairs that an indi vidual had. These permanentdye mixtures employ a specific dye composition which is oxidized by anoxidizing agent while applied to ones hair to impart a particular colorthereto. On hair that is less than 75% gray, these permanent dyemixtures are not particularly useful. since the coverage result is anundesirable darker shade and/or the oxidation reaction is so great thatit actually lightens the naturally colored hair by bleaching and damagesthe naturally colored hair.

Another difficulty encountered with the use of the permanent dyemixtures is the take of the dye on damaged hair. The hair on the head ofa modern woman is repeatedly shampooed. treated with a wide assortmentof cosmetics from aerosol hair sprays and setting solutions to permanentwaving products. This causes the ends of the hair, which are the olderhair, to become damaged." since they are more porous and absorptive.possess less luster. and are inclined to tangle. This damaged conditionis further accentuated by exposure to sunlight, especially if the hairhas been treated with an oxidizing agent through such treatments asblecahing. dyeing or permanent waving. Since the porosity of each strandof damaged hair varies throughout the length of the strand, portions ofeach strand of hair will absorb larger amounts of dye and will possessan entirely different color than the less absorptive portions of thehair strand. This produces color streaks and an unnatural appearanceunless special methods are used.

In order to cause the oxidative hair-dye composition to react and impartcolor to the hair. an oxidizing agent must be present. Generally. a 6percent solution of hydrogen peroxide in water is employed. Thishydrogen peroxide solution is difficult to handle since it may reactwith the skin of the individual applying the haircoloring mixture.Generally. the hydrogen peroxide solution will cause a whitening orblanching of the skin which is also accompanied by a painful. stingingsensa tion which persists for several minutes. This undesirableblanching and painful stinging sensation are associated by thehairdresser or user with hair damage.

Women who are in the transition stage. whose naturally colored hair isgradually acquiring gray strands. sough other methods of coloring theirhair to amid the inherent difficulties encountered with the permanentdye mixtures. The products employed by most women who desire coverae ofa few gray strands hair coloring rinses. While these products do pronsufficient coloring for the few gray strands in an individuals head ofhair. the color is relatively easily washed out with normal shampooing.Furthermore. the desired coverage is not achieved when the quantity ofgray hair exceeds 10%.

In order to satisfy the requirements for women who have 10 to percentgray hairs. a semi-permanent dye product has been developed. Generally,these semi-permanent products comprise aqueous solutions ofnitrophenylene diamines or similar nitro benzenoid amines or nitro aminophenols. together with dispersed colors. The major faults of theseproducts are that the color does not remain true. and undesirable shadesdevelop in sunlight or even with repeated shampoos. Also. the colortends to fade rapidly. The most objectionable problem that exists withthese semi-permanent dyes is the fact that porous hair and hair that hasbeen permanently waved will accept the colors very rapidly and/or willpreferentially select one of the coloring ingredients. Consequently.unnaturally streaked or colored hair sections frequently occur.

OBJECTS OF THE INVENTION It is an object of this invention to provide ahaircoloring mixture which is capable of conditioning the hair as wellas coloring it.

Another object of this invention is to provide a haircoloring mixture ofthe above character that substantially reduces or eliminates skindiscomfort during application.

Another object of this invention is to provide a haircoloring mixture ofthe above character that imparts unfading natural colors which arehighly resistant to light and shampoo. even with prolonged wear andrepeated shampoos.

A further object of this invention is to provide a haircoloring mixtureof the above character that does not produce off shades or streaky colorsections. either during or after application thereof.

Another object of this invention is to provide an oxidizing agent thatdoes not produce the blanching or stinging effects of hydrogen peroxide.

Another object of this invention is to provide a haircoloring mixture ofthe above character which will not damage the hair to which it isapplied, while imparting a high gloss and smooth feel thereto.

Another object of this invention is to provide a haircoloring mixture ofthe above character which provides excellent uniformly leveled colorthroughout the hair regardless of the damaged character or porosity ofthe hair.

Other and more specific objects will be apparent from the features.elements. combinations and operating procedures disclosed in thefollowing detailed description.

SUMMARY OF THE INVENTION The hair-coloring mixtures of this inventionsubstantially reduce or completely eliminate the inherent problemsassociated with prior art hair-coloring mixtures by employing one ormore of the hair-coloring mixture additives that we have developed. Byadding milk or beer as a partial substitute for a portion of theoxidizing agent employed in the hair-coloring mixture, distinct andunexpected advantages are produced. Additional partial substitutes oradditives for the oxidizing agent which substantially improve prior arthair-coloring mix tures are viscosityimparting ingredients. Theinclusion of viscosity-imparting ingredients in the oxidizing agentprovides conditioning to the hair while also producing an oxidizingagent that is more easily handled and up plied. The inclusion of milk orbeer in the hair-coloring mixture also conditions the hair and therebyallows the coloring to take more uniformly throughout.

As a substitute for the commonly used oxidizing agents, we havedeveloped a new oxidizing agent for use in hair-coloring. This oxidizingagent comprises a hydrogen/ peroxide yielding compound in solution witha polyhydroxy alcohol. Preferably, an aqueous solution of hydrogenperoxide or solid urea peroxide is dissolved in a polyhydroxy alcohol,such as glyccrine andlor propylene glycol, in sufficient percentages toprovide an available hydrogen/peroxide yeilding compound concentrationof about 8 percent by weight. This oxidizing agent has been found to becompletely safe and more easily handled by the user, since skinblanching and stinging are substantially reduced. Since the annoying,undesirable effects of normally used hydrogen peroxide yielding solutionare substantially re duced or eliminated, the hairdresser or user findsthe oxidizing agent of this invention much more desirable to use, anddoes not associate hair damage with this oxidizing agent.

The various hair-coloring mixture additives of this invention can beemployed separately with prior art hair-coloring mixtures or asindividual or multiple substitutes for some of the ingredients of theprior art haircoloring mixtures without departing from the scope of theinvention.

The invention accordingly comprises the features. elements, combinationsand operating procedures hereinafter disclosed, and the scope of theinvention will be indicated in the claims.

DETAILED DESCRIPTION The hair-coloring mixture of this inventionprevents the normal damaging action of dyeing hair with oxidativehair-dye compositions and oxidizing agents while also improving thecondition of the hair by substituting milk or beer for part of theconventional water solution of the oxidizing agent. Although milk isbeing used broadly to include all natural and synthetic liquids whichresemble milk, whole fresh milk is the preferred additive. It isbelieved that the high protein content of these liquids provides anexcellent protective and re medial action upon hair, since hair is alsoa protein. Whole milk is the preferred liquid for use in thehaircoloring mixture of this invention due to the fact that whole milkcontains suspended lipoidal ingredients, making it similar to thesurface of the hair, which is believed to consist of lipo-proteins.

In most hair coloring applications, the oxidizing agent employed is asolution of hydrogen peroxide or urea peroxide in water. Thehydrogen/peroxideyielding compound concentration usually comprises 6percent by weight of the solution or, as is known in the art, 20 volumeperoxide." The term 20 volume peroxide" indicates the quantity ofperoxide in solution, which will produce a quantity of oxygen that istwenty times greater in volume than the voiume of the peroxide solution.Throughout this disclosure, all percentages relating to the hair colormixture and its constituents are weight percentages.

We have found that the beneficial action provided by the incorporationof milk or beer is present even when the concentration of the hydrogenperoxide or urea peroxide is substantially increased above the levelusually used in commercial practice. To substantiate this point, a l2percent aqueous solution of hydrogen peroxide or 40 volume peroxide,instead of the usual 6 percent hydrogen peroxide, was prepared and usedfor dyeing. The hair coloring was excellent and the conditioning actionwas clearly evident.

We have also found that even at peroxide concentrations substantiallylower than commercial levels, the presence of the milk or beer providesa leveling and protective effect and allows the dye to provide a verynatural hair color, substantially reducing or eliminating damaged andporous sections of the hair from grabbing" the dye and therebydeveloping more intense and darker colors. Furthermore, the surface ofthe hair is more lustrous, smoother to the touch, and easier to comb andarrange into a coiffure. More importantly, a significant stiffness isimparted to the hair so that the dry coiffure has more body, especiallywhen whole milk is employed.

Virtually any commercially available oxidative hairdye composition canbe successfully employed in the hair-coloring mixture of this invention.Such oxidative haindye compositions generally compriseparabenzenoid-diamines, couplers, wetting and foaming agents,viscosity-controlling agents, antioxidants, ammonia, isopropyl and/orethyl alcohol, and water. Some typical oxidation dye formulations areshown below in TABLES l and II, and were obtained from the AmericanPerfumer and Cosmetics magazine, page 6l, Vol. 83, October 1968.

TABLE I.

OXIDATION DYE FORMULATIONS lntennediates Dark Light & Chemicals BlackBrown Brown Auburn Blond Grey para-phenylenediamine 2.70 0.80 0.56 0.080. l S 0. l 5 resorcinol 0.50 1.60 0.80 0. I0 I00 0.80 para-aminophenol0.20 0.20 0.20 0. l5 ortho-aminophenol 0.20 1.00 0.28 0.04 0.20 2,4-diaminoanisol sulfate 0.40 0.0l 0.07 nitropara-phenylenediamme 0.040.40 0,04 2-nitro-4-aminophenol 0.40 oleic acid 20.0 20.0 20.0 20.0 20.020.0 oleyl alcohol [5.0 l5.0 15.0 l5.0 l5.0 [5.0 Solulan 5* 3.0 3.0 3.03.0 3.0 3.0

A LE 1- -Continued OXIDATION DYE FORMULATIONS intermediates Dark Light64 Chemicals Black Brown Brown Auburn Blond Grey propylene glycol 12.0120 12.0 12.0 12.0 12.0 isopropyl alcohol 10.0 10.0 10.0 10.0 10.0 l0.0Hampene 100 0.5 0.5 0.5 0.5 0.5 0.5 sodium sulfate 0.5 0.5 0.5 0.5 0.50.5 ammonium hydroxide (28%) 10.0 10.0 10.0 10.0 10.0 10.0 water(dc-ionized) 19.0 19.0 19.0 19.0 19.0 19.0

Solulan S 5 mole ethyoxylated lanolin alcohols (American Cholesterol.Edison. NJ] Hampene I Ethylene diamine tetracetic acid Na (New HampshireChem. Div. W. R. Grace. Nashua. NH] All weights are given in grams. Thecorrect amount of dye is dissolved in the propylene glycol by heating.The oleic acid and Solulan 5 are mixed together and the dye solutionadded to this mixture with stirring. The oleyl alcohol is dissolved inthe isopropyl alcohol and added to the mixture with stirring. Next. theammonium hydroxide is added folloued by the Hampene and sodium sulfatedissolved in the water.

TABLE 11 OXIDATION DYE FORMULATIONS TONERS Intermediates Platinum AshGold Red & Chemicals Platinum Silver Smoke Blond Blond Blond Blondpara-phenylenediamine 0.08 0.06 0.10 0.05 0.06 para-toluylenediaminesulfate 0.10 0.04 0.08 resorcinol 0.50 0.02 0.08 0.08 0.70 0.40pyrogallic acid 0.04 0.40 para-aminophcnol 0.08 0.04 2. 4-diaminoanisolsulfate 0.04 0.05 0.04 0.02 0.01 2 nitro-4-aminophcnol 0.002 0.02 0.040.20 nitropara-phenylenediamine 0.02 0.008 0.02 6-chloro4-nitro-Z-aminophenol 0.04 4-nitroortho-phenylene diamine 0.03 oleic acid 20020.0 20.0 20.0 20.0 20.0 20.0 Ethomeen S 12* 9.0 9.0 9.0 9.0 9.0 9.0 9.0Cerasynt 303* 6.0 6.0 6.0 6.0 6.0 6.0 6.0 propylene lycol 12.0 12.0 12.012.0 12.0 12.0 12.0 isopropyl a cohol l0.0 10.0 10.0 10.0 10.0 100 10.0Hampene 100*" 0.5 0.5 0.5 0.5 0.5 0.5 0.5 sodium sulfate 0.5 0.5 0.5 0450.5 0.5 0.5 ammonium hydroxide (28%) 10.0 10.0 10.0 10.0 10.0 10.0 10.0water (dc-ionized) 22.0 22.0 22.0 22.0 22.0 22.0 22.0

'Ethomeen S- 12 Bis-Z-hydroxyethyl soybean amine (Armour IndustrialChemical Co.. Chicago. Ill.)

Cerasynt 303 Hydroxyethyl stearyl amide (Van Dyk. Belleville. NJ.)

'"Hampene Ethylene diamine tetracetic acid Na, (New Hampshire ChemicalCompany, Nashua. NH.) All weights are given in grams. The method ofdissolving is the same as in Table 1. except that the oleic acid.Ethomeen 5-12. and Cerasy nt 303 are melted together until uniform. andthen the propylene glycol solution of the dye is added.

Oxidation dye compositions of this type are already known to theexperts. Typical formulas which can be used are disclosed in U.S. Pat.No. 3,561,912, issued to Boosen et al., and U.S. Pat. No. 3,563,684,issued to Charle et a]. Other typical formulas are listed in SagarinsCosmetics. Science and Technology," lnterscience Publishers, Inc., NewYork 1957, on pages SO35 12. Other typical oxidative dye compositionsare described in a series of articles titled Technology of ModernOxidation Hair Dyes by Gus S. Kass in the American Perfumer, seeparticularly Part 1, July 1956, pages 27 and 28, and Part 111, September1956, pages 48 and 49. Some well-known commercial dye compositions whichare representative of this type of oxidative hair-dye compositions andcan be employed in the haircoloring mixtures of this invention areVitacolor." manufactured by Zotos International. lnc.; Miss Clairol."manufactured by Clairol, lnc.; Color Charm" manufactured by Well-a,Inc.; and similar dyes manufactured by Revlon and LOreal.

When the white hair of a particular individual is at least three timesthe number of naturally colored hair, generally referred to in the tradeas gray, complete dye coverage is required and the hydrogen peroxideconcentration generally used in the trade is 6% or higher, providedsubstantially equal quantities of oxidative hair-dye compositions andoxidizing agents are intermixed.

In order to compare the hair-coloring mixture of this invention with thehair-coloring mixtures normally used for coverage of a 75% gray head ofhair. the following experiment was performed. One ounce of ZotosVitacol0r" V-Sl Raven Black, an oxidative hair-dye composition, and oneounce of a 6 percent solution of hydrogen peroxide in water (20 volumehydrogen peroxide) were intermixed and applied to half the head of hair.The other half of the head of hair was dyed with a hair-coloring mixturecomprising one ounce of the same oxidative hair-dye composition. onehalf ounce of whole milk, and one half ounce ofa 12 percent solution ofhydrogen peroxide in water (40 volume hydrogen peroxide). The two sidesof the head were equally intense in color, but the side dyed with thehair-coloring mixture containing the milk was more evenly colored fromthe scalp to the ends of the hair, while also being more lustrous,easier to comb, and the set coiffure when dry had more body.

Similarly, experiments involving other dye intermediate compositions,shown in Table III below, produced substantially identical results.Regardless of the particular coloring shade desired or the oxidativehair-dye composition employed, more desirable hair coloring was providedwhen the hair coloring mixture contained the milk.

bleaching. By incorporating milk or beer into the semipermanenthair-coloring mixture of this invention, more natural and lustrouscolors and more manageable hair are achieved.

The preferred hydrogen peroxide-yielding compound concentration in thesemi-permanent hair-coloring mixture to be applied to the hair is about0.35 percent by weight. This concentration of the available hydro genperoxide-yielding compound is the same whether an aqueous solution ofhydrogen peroxide or powdered urea peroxide is employed. We have foundthat at eoncentration levels below 0.2 percent by weight, the colordevelopment is too slow to be effective, and with hydrogenperoxide-yielding compound concentrations TABLE Ill COMMERCIALLYAVAILABLE OXIDATIVE HAIR-DYE COMPOSITIONS Miss Clairol L'Oreal RouxShade Hair Color lmedia Par Wella Fanci-Tone Helene Curtis RevlonGrouping; Vitacolor Bath Excellence Color Charm Creme Tint Color-essenceSoft Tint Ash V42 42 6 542 I6 23 Blondes August Moongold Lt. Brown AshBlonde Hidden Lt. Brown Ultra Ash Moon Honey Med. Blonde V45 45 66 4453l 44 7 Reds Russet Sparkling Lt. Auhum Lt. Auburn Dark Lt. AuburnCherry Sherry Blaze Warm V57 57 257 3l 8A Browns Cafe Coffee Dark GoldenDark Warm Chestnut Brown Brown Brown Brown V51 5| 1 U5l 12 2O [2 BlackRaven Black Blue Black Black Black Deep Black Ebony Black Velvet RageSemi-Permanent Hair Coloring For women who are going gray and have lessthan 75 percent gray hairs and preferably less than 50 percent, oursemi-permanent dyeing composition provides beautifully natural,non-fading colors which are highly resistant to light and shampoo, anddo not develop off shades or streaky color sections even with prolongedwear and repeated shampooing. We have also found that on women who aregoing gray a much more natural appearance is achieved if completecoverage is avoided. The natural appearance desired can be achieved bymaintaining the hydrogen peroxideyielding compound concentration in themixture applied to the hair between 0.2 and l percent by weight. Theresults, however, are generally improved when milk or beer isincorporated into the hair-coloring mixture.

By applying a hair-coloring mixture with substantially lower peroxidelevels than normally employed in the trade, either with or without theuse of milk or beer, a unique hair-coloring mixture is provided for thecoloring of hair on heads which are merely going gray. The lowerperoxide level substantially eliminates bleaching of the naturallycolored hair while providing sufficient oxidation of the oxidativehair-dye composition and coloring only the graying hairs. Consequently,the advantages of a permanent dye such as its resistance to repeatedshampooing, prolonged wear, and stability to light are provided in asemi-permanent haircoloring mixture while avoiding the disadvantages ofpermanent and semi-permanent hair-coloring mixtures such as streakycolor sections, off shades, and hair greater than l percent by weight,the coverage becomes too great to adhieve naturalness and the naturalcolored hair is lightened as well as damaged. By preventing damage tothe hairs natural appearance" and substantially reducing or eliminatingareas where deeper color formation occurs, the new growth of the naturalcolored hair will not result in color variations. This reduces therapidity with which touch-up applications are required, depending uponthe relative amount of gray hairs.

[n the final hair-coloring mixture to be applied to the hair comprisingthe oxidative hair-dye composition, the milk or beer and the oxidizingagent, the concentration of the milk or beer preferably ranges fromabout 25 to percent by weight. If the concentration is greater than 75percent by weight, the color imparted to the hair will tend to be toolight; and if the concentration is less than 25 percent by weight, theimproved even color, luster and body are not obviously present. Also,when low concentrations of milk or beer are employed, it is desirable toreduce the concentration of the oxidative hair-dye composition in thefinal hair coloring mixture to approximately 50 percent in order toprevent the developed hair color from becoming too dark. Thisconcentration reduction is best achieved by merely adding a requiredamount of water to the hair-coloring mixture. In the preferredembodiment, whole fresh milk is used. However, skimmed milk, evaporatedor dried milk powder, or synthetic milk-like products can be used withequal efficacy as long as their approximate solid content issubstantially the same as whole fresh milk.

Once the hair-cvlering mixture has been prepared, the mixture ispreferably poured into a clean plastic applied bottle and immediatelyapplied to the hair. Preferably, the mixture is first applied to thehair closest to the scalp without sectioning the hair. Then, the mixtureis applied to the rest of the hair and worked throughout the hair as ashampoo, without massaging the mixture into the scalp.

A sufficient amount of time is then allowed to elapse until proper colordevelopment is achieved. Generally, from to 35 minutes will be requiredfor proper color development; however, various conditions and/or the useof well known methods can substantially alter the required time. Whenthe desired color is achieved, water is added to the hair in sufficientquantity to work the hair-coloring mixture into a lather. The lather isspread throughout all the hair and then rinsed out with waterimmediately.

When previously colored hair is being retouched, the hair-coloringmixture is applied generously to the new growth only. If the hair shaftsand ends have enough color from previous treatments, the hair-coloringmixture is not applied thereto. If the previously colored hair is faded,dry, porous or permanently waved, the remaining hair-coloring mixtureshould be diluted with an equal amount of shampoo and then blendedthroughout all the hair.

Oxidizing Agent One of the major difficulties encountered with all haircoloring mixtures that require a source of oxidation is the inherentproblems associated with hydrogen peroxide and urea peroxide. These twocompounds have been found to be the best source of oxidation forhair-coloring purposes, but do possess well known stability and handlingproblems, and have characteristics that are distinguished by thehairdresser or the user as damaging to the hair. We have found thatvirtually all the difficulties and undesirable characteristics encountered with the use of hydrogen peroxide and urea per oxide aresubstantially reduced or eliminated by providing a solution of hydrogenperoxide or urea peroxide in a polyhydroxy alcohol, such as glycerineand/or propylene glycol. The hydrogen peroxide-yielding compounds havebeen found to be sufficiently stable in the presence of the polyhydroxyalcohols, and the presence of a polyhydroxy alcohol in the hair-coloringmixture has been found not to interfere with the reaction of thehydrogen peroxide-yielding compound and the oxidative hair-dyecomposition, but instead supplements the hair-coloring operation byproviding a further conditioning action.

The solution of urea peroxide in an anhydrous polyhydroxy alcohol isparticularly advantageous because of the difficulties involved with theuse of urea peroxide. When the powdered form of urea peroxide is addeddirectly to the oxidative hair-dye composition, complete mixture isdifficult to obtain and oxidation of the dye composition beginsimmediately, before all the urea peroxide powder has been dissolved.Furthermore, solid crystals may fall to the bottom of the hair coloringmixture, thus becoming inactive or if shaken may plug the nozle 0f theapplicator. Also, sloid urea peroxide is not always sufficiently stablefor a commercial product when subjected to the wide variations intemperature and humidity found in warehouses and the market shelves. Thewater solution of urea peroxide has been found to be even less stablethan the powdered form and is avoided in the trade.

The solution of urea peroxide in the anhydrous polyhydroxy alcohol hasbeen found to be completely stable am? fully employablc in all oxidizinghair-coloring mixturcs. The only limitation found with urea peroxide isits upper solubility limit, such as 17 percent in propylent) glycol atroom temperature.

A solution of hydrogen peroxide in a polyhydroxy alcohol has theadvantage of achieving higher concentrations than is possible with ureaperoxide. This advantage is important when equal amounts of theoxidative hair-dye composition and milk or beer are used, since thehydrogen peroxide-yielding compound concentration in the polyhydroxyalcohol must be sufficiently high to assure proper oxidation of theoxidative hair dye composition to achieve the desired intensity of thedeveloped color.

Solutions of hydrogen peroxide in polyhydroxy alcohols have been foundto be suffieiently stable, with the undesirable characteristics andproperties of aqueous solutions of hydrogen peroxide substantiallyreduced or completely eliminated. One of the most important advantagesof these polyhydroxy alcohol solutions is the elimination of whiteningor blanching action on many skins. An 8 percent solution of hydrogenperoxide in a polyhydroxy alcohol did not produce a whitening orblanching action on most skins, while a 6 percent aqueous solution ofhydrogen peroxide did produce a whitening or blanching action on mostskins. Even on skins where a blanching reaction did occur with thehydrogen peroxidepolyhydroxy alcohol solutions, the time before skinblanching occurred was substantially increased. In most hair treatmentoperations, the hydrogen peroxide-polyhydroxy alcohol solutions willhave been diluted or removed before the more sensitive skins will beblanched.

The substantial reduction or elimination of skin blanching is extremelyimportant since a painful stinging sensation which persists for severalminutes accompanies the skin blanching. To the hairdresser or user, theelimination of painful stinging and blanching is an important advantagesince hair damage is associated therewith. Consequently, an oxidizingagent which comprises a solution of a hydrogen peroxide-yieldingcompound in a polyhydroxy alcohol represents a unique advancement in thehair treatment field and possesses great marketing potential.

In our preferred embodiment for the oxidizing agent, the concentrationof the polyhydroxy alcohol is maximized, since the polyhydroxy alcoholdoes impart a conditioning action to the hair while also being ahumectant. The fact that the polyhydroxy alcohol is a humectant isextremely important since this property slows or prevents waterevaporation on the skin, thereby preventing the hydrogen peroxide frombecoming concentrated thereon. Consequently, blanching and stinging doesnot occur on most skins.

These solutions of either urea peroxide or hydrogen peroxide in thepolyhydroxy alcohol have the added desirable characteristic of beingoily and viscous. This oily, viscous characteristic provides the user ofthe hair-coloring mixture with a feeling of increased conditioning.

The lower the water content, the more oily and viscous the solution willbe. However, normally aqueous hair-coloring mixtures can be made moreviscous by incorporating viscosity-imparting materials in the aqueousoxidizing agents. However, most viscosity imparting material will makethe hydrogen peroxide yielding compound in the aqueous oxidizing agentless TABLE Iv PREFERRED OXlDlZlNG AGENTS Composition Relative WeightPercent \l .2 stable, unless the viscosity-imparting material is one sesFormul 1 Formula lected from the group consisting of carboxy methylcelhydrogen peroxide 7'9 lulose, methyl cellulose. hydroxyethylcellulose, and 14:,

. I t Nil C polyvmylpyrrolidone. The incorporation of aviscositypropylene 75 79 33445 imparting material in the oxidizing agentsubstantially TABLE V HAlR-COLORING MIXTURES A B C D E Quantity 7rQuantity 71 Quantity 1' Quantity 71 Quantity (02.) Wgt/Vol. (01.)Wgt/Vol. toz.) Wgt/Vol. (02.) Wgt/Vol. (02.) Wgt/Vol.

Oxidative hair dye composition 2 50 2 50 2 50 2 50 2 50 Oxidizing agentlie 2 2/3 U6 U6 available hydrogen peroxide yielding compound .34 .351.0 .25 .34 water .68 49.65 l5.6 3.82 polyhydroxy alcohol 3.22 3.85viscosity imparting material 0.08 Milk l-S/o 45.8 l-l/3 33.4 l-5/6 45.8l-S/fi 45.8

In Mixture A. the oxidizing agent is an 3% solution of [4,0 in propyleneglycol. ln Mixture B. the oxidizing agent is an 0.77r solution of H.101in water. in Mixture C. the oxidizing agent is a 6% solution of Hf) inwater. In Mixture D, the oxidizing agent is n I791 solution of ureaperoxide in propylene glycol [equivalent to (xl'ii H 0 ln Mixture E. theoxidizing agent is an 8'1 solution of H,O, 8r. 2; hydroxy methylcellulose aqueous vehicle.

improves the handling characteristics of the oxidizing EXAMPLES agentwhile conditioning the hair to obtain more natural colors.

Some persons skilled in the art may believe that an oxidizing agent suchas hydrogen peroxide when dissolved in an organic liquid such as apolyhydroxy alcohol would be hazardous. However, independent tests wereperformed and it was discovered that a saturated sollution of ureaperoxide and propylene glycol and a 24 percent solution of hydrogenperoxide in propylene glycol were not explosively hazardous. Thehydrogen peroxide solution tested was prepared by dissolving a percentaqueous solution of hydrogen peroxide in propylene glycol.

The preferred oxidizing agent compositions of this invention comprises ahydrogen peroxide composition prepared by dissolving a sufficientquantity of a 35 percent aqueous solution of hydrogen peroxide inpropylene glycol to provide an 8 percent available hydrogen peroxideconcentration. Generally, 23.3 kilograms ofa 35 percent aqueous solutionof hydrogen peroxide is dissolved in sufficient propylene glycol toobtain a final volume of 100 litres. In Table IV the compositions of thetwo preferred oxidizing agents are presented. Hydrogen peroxidestabilizers, well known in the art, may be added to these solutions ofhydrogen peroxideyielding compounds in the polyhydroxy alcohol toimprove the hydrogen peroxide-yielding compounds stability in storage.We have also found that these solutions may be stored in glass; however,plastic containers are preferred. In summary, Table V presents vari oushair-coloring mixtures of this invention; and, in the examples thatfollow, the many distinct advantages of some of these mixtures arestates.

The following examples of our invention in use are presented forillustrative purposes only, and are not intended to be used in alimiting sense.

1a. A hair-coloring mixture of the following:

2 oz. Ash Blonde shade of VitaColor V-42 August Moon," a trademarked dyeproduced by Zotos lnternational, lnc., and

2 oz. of a 0.7 percent aqueous solution of hydrogen peroxide was appliedfor 30 minutes to a head of clean brown hair that was 25 percent gray,"and then shampooed out and dried. The hair appeared natural. since thepigmented hair was not lightened and the white hair was colored to thenatural brown color. Also, the hair was not damaged, as indicated by ahigh 20 percent index of 095-1, using an lnstron Tensile Tester. Thistest for hair damage is well known in the art and indicates thecomparative strength of the treated hair with untreated hair whenstretched 20% of its initial length lb. By comparison, when the same 25percent gray head of hair was treated in the same way for the same timewith a hair-coloring mixture comprising:

2 oz. of Vitacolor V-42 August Moon, and

2 oz. of a 6 percent aqueous solution of hydrogen peroxide,

the natural pigmented hair was bleached and resulted in an overallunnatural appearance. Also, the hair was damgaged, as indicated by the20 percent index being 0.70-0.80, using an lnstron Tensile Tester.

lc. A hair-coloring mixture comprising:

1-5/6 oz. of whole milk,

l/6 oz. of an 8 percent aqueous solution of hydrogen peroxide, and

2 oz. of Vitacolor V-42 August Moon was applied in the manner describedabove in Example l(a The hair showed a higher gloss and smoother feel tothe touch than was evident in Examples 1(a) and l(b). These effects wereeasily observed by one skilled in the art. Furthermore, there was nodamage to the hair, as indicated by a high 20 percent index of 0.95using an lnstron Tensile Tester.

1d. Ash Blond hair such as in the above examples was permanently wavedand then two months later was colored by halfhead techniques with theSemi-Permanent hair-coloring Loving Care Ash Blonde No. 73, marketed byClairol, and the other half with the haircoloring mixture employed inExample l(c). Part of the hair was non-porous new growth and part wasporous from the permanent wave. The results showed that thehair-coloring mixture of Example l(c) produced excellent, leveledcoloring with the color on the new growth (non-porous hair)substantially identical to the color on the porous section of hair. TheLoving Care side was unevenly colored, with the porous (permanentlywaved) area having a different shade than the non-porous area.

2a. A hair-coloring mixture of the following:

2 oz. of the same Vitacolor Ash Blonde shade as used in Example 1 above,

1-5/6 oz. of milk, and

1/6 oz. of 8 percent hydrogen peroxide in propylene glycol (made bydissolving 23.3 Kg. of 35 percent hydrogen peroxide in sufficientpropylene glycol to made 100 litres). The hair-coloring mixture wasapplied on the same type of hair as in Example l(a) above. The resultsin all respects were similar to those obtained in Example l(c) above,but the hairdresser preferred to use this mixture and stated that sheexperienced no blanching or tingling action from contact with thepropylene glycol solution, and liked its conditioning effect on thehair.

In place of the Viatcolor 42 August Moon, which is an Ash blonde shade,we have also done the same experiments on graying heads having naturallydifferent colored hair. For example, we have used Vitacolor V-45 Russetfor a head containing 65 percent natural red colored hair, and VitacolorV-57 Cafe Brown for a head containing 75 percent warm brown natural colored hair, and Vitacolor V-Sl Raven Black" on a head having 80 percentnatural black colored hair. The results were the same except for theshades of color produced.

The same superior results were obtained with the hair coloring mixtureof our invention when we used dyes or tints from other commercialsources. In Table 1 above, the trade marked items from other commercialsources similar to the four Vitacolor shades noted above are presented.

It will thus be seen that the objects set forth above, among those madeapparent from the preceding description, are efficiently attained and,since certain changes may be made without departing from the scope ofthe invention, it is intended that all matter contained in the abovedescription shall be interpreted as illustrative so as to obtain thebenefit of all equivalents to which the invention is fairly entitled.

It is also to be understood that the following claims are intended tocover all of the generic and specific features of the invention hereindescribed, and all statements of the scope of the invention which, as amatter of language, might be said to fall therebetween.

Having described our invention, what we claim as new and desire tosecure by Letters Patent is:

l. A hair-coloring mixture comprising:

A. between about 25 and percent by weight of an aqueous oxidativehair-dye composition;

B. between about 0.1 and 50 percent by weight of an oxidizing agentcomprising a hydrogen peroxideyielding compound selected from the groupcon sisting of hydrogen peroxide and urea peroxide and an aqueouscarrier; and

C. between about 25 and 75 percent by weight of a conditioning agentselected from the group consisting of milk and beer.

2. The hair-coloring mixture as defined in claim 1 wherein said aqueouscarrier further includes a viscosity-imparting ingredient selected fromthe group consisting of methyl cellulose, hydroxyethyl cellulose,carboxy methyl cellulose, and polyvinylpyrrolidone.

3. The hair-coloring mixture as defined in claim 1, wherein the hydrogenperoxide-yielding compound of said oxidizing agent has a concentrationbetween about 0.2 and 1 percent by weight of the total hair-coloringmixture.

4. The hair-coloring mixture as defined in claim 1 wherein the hydrogenperoxide-yielding compound of said oxidizing agent has a concentrationof about 0.35 percent by weight of the total hair-coloring mixture.

5. The hair-coloring mixture as defined in claim I, wherein the aqueouscarrier further includes a polyhydroxy alcohol selected from the groupconsisting of glycerine and propylene glycol.

6. A hair-coloring mixture comprising:

A. between about 25 and 75 percent by weight of an aqueous oxidativehair-dye composition; and

B. between about 25 and 75 percent by weight of an oxidizing agentcomprising a hydrogen peroxideyielding compound selected from the groupconsisting of urea peroxide and hydrogen peroxide and an aqueous carriercontaining a polyhydroxy alcohol selected from the group consisting ofglycerine and propylene glycol.

7. The hair-coloring mixture as defined in claim 6, wherein the hydrogenperoxide-yielding compound of said oxidizing agent has a concentrationbetween about 0.2 and 1 percent by weight of the total hair-coloringmixture.

8. The hair-coloring mixture as defined in claim 6, wherein the hydrogenperoxide-yielding compound of said oxidizing agent has a concentrationof about 0.3 percent by weight of the total haircoloring mixture.

9. A method for coloring the hair on a human head comprising the stepsof A. applying a hair-coloring mixture comprising be tween about 25 and75 percent by weight of an aqueous oxidative hair-dye composition;between about 0.1 and 50 percent by weight of an oxidizing agentcomprising a hydrogen peroxide-yielding compound selected from the groupconsisting of hydrogen peroxide and urea peroxide and an aqueouscarrier; and between about 25 and 75 percent by weight of a conditioningagent selected from the group consisting of milk and beer to the hair;and

B. allowing sufficient time for color development.

10. A method for coloring hair on a human head comprising the steps of:

A. applying a hair-coloring mixture comprising between about 25 and 75percent by weight of an aqueous oxidative hair-dye composition; betweenabout 0.1 and 50 percent by weight of an oxidizing agent comprising ahydrogen peroxide-yielding compound selected from the group consistingof hydrogen peroxide and urea peroxide and an aqueous carrier containinga viscosity imparting ingredient selected from the group consisting ofmethyl cellulose, hydroxyethyl cellulose, carboxy methyl cellulose, andpolyvinylpyrrolidone, and between about 25 and 75 percent by weight of aconditioning agent selected from the group consisting of milk and beerto the hair; and

B. allowing sufiicient time for color development.

1 l. A method for coloring the hair on a human head comprising the stepsof:

A. applying a hair-coloring mixture comprising bepropylene glycol to thehair; and

B. allowing sufficient time for color development.

CERTIFICATE OF CORRECTION Patent: No. 3'898'032 Dated August 5 1975lnventofls) Walter W. Edman and Ralph L. Evans, Jr.

It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 1, Line 45 "blecahing" should be bleaching Column 2, Line 3,"coverae" should be coverage Column 3, Line 15, "hydrogen/peroxideyielding"should be hydrogen peroxide-yielding Column 3, Line 20,"hydrogen/peroxide yeilding" should be -hydrogen peroxide-yieldingColumn 4, Line 9, "hydrogen/peroxide yielding" should be hydrogenperoxide-yielding Column 8, Line 36, "adhieve" should be achieve Column9, Line 2, "applied" should be applier Column 9, Line 64, "nozle shouldbe nozzle "sloid" should be solid Column 12, Line 39,"la." should be1(a) Column 12, Line 55,"lb." should be 1(b) Column 12, Line 65,"lc."should be 1(c) Column 13, Line 9, "1d." should be 1(d) Column 13, Line24,"2a." should be 2(a) Page 2 UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent No. 3,898,032 Dated August 5 3 1975 Walter W. Edmanand Ralph L. Evans, Jr. Inventor (s) It is certified that error appearsin the above-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 13, Line 39, "Viatcolor" should be Vitacolor Column 14, Line 53,"0.3" should'be 0.35

Signed and Scaled this Attest:

RUTH C. MASON C. MARSHALL DANN Arlesling Officer Commissioner of Parentsand Trademark

1. A HAIR-COLORING MIXTURE COMPRISING: A. BETWEEN ABOUT 25 AND 75PERCENT BY WEIGHT OF AN AQUEOUS OXIDATIVE HAIR-DYE COMPOSITION, B.BETWEEN ABOUT 10.1 AND 50 PERCENT BY WEIGHT OF AN OXIDIZING AGENTCOMPRISING A HYDROGEN PEROXIDE-YIELDING COMPOUND SELECTED FROM THE GROUPCONSISTING OF HYDROGEN PEROXIDE AND UREA PEROXIDE AND AN AQUEOUSCARRIER, AND C. BETWEEN ABOUT 25 AND 75 PERCENT BY WEIGHT OF ACONDITIONING AGENT SELECTED FROM THE GROUP CONSISTING OF MILK AND BEER.2. The hair-coloring mixture as defined in claim 1 wherein said aqueouscarrier further includes a viscosity-imparting ingredient selected fromthe group consisting of methyl cellulose, hydroxyethyl cellulose,carboxy methyl cellulose, and polyvinylpyrrolidone.
 3. The hair-coloringmixture as defined in claim 1, wherein the hydrogen peroxide-yieldingcompound of said oxidizing agent has a concentration between about 0.2and 1 percent by weight of the total hair-coloring mixture.
 4. Thehair-coloring mixture as defined in claim 1 wherein the hydrogenperoxide-yielding compound of said oxidizing agent has a concentrationof about 0.35 percent by weight of the total hair-coloring mixture. 5.The hair-coloring mixture as defined in claim 1, wherein the aqueouscarrier further includes a polyhydroxy alcohol selected from the groupconsisting of glycerine and propylene glycol.
 6. A hair-coloring mixturecomprising: A. between about 25 and 75 percent by weight of an aqueousoxidative hair-dye composition; and B. between about 25 and 75 percentby weight of an oxidizing agent comprising a hydrogen peroxide-yieldingcompound selected from the group consisting of urea peroxide andhydrogen peroxide and an aqueous carrier containing a polyhydroxyalcohol selected from the group consisting of glycerine and propyleneglycol.
 7. The hair-coloring mixture as defined in claim 6, wherein thehydrogen peroxide-yielding compound of said oxidizing agent has aconcentration between about 0.2 and 1 percent by weight of the totalhair-coloring mixture.
 8. The hair-coloring mixture as defined in claim6, wherein the hydrogen peroxide-yielding compound of said oxidizingagent has a concentration of about 0.3 percent by weight of the totalhair-coloring mixture.
 9. A method for coloring the hair on a human headcomprising the steps of A. applying a hair-coloring mixture comprisingbetween about 25 and 75 percent by weight of an aqueous oxidativehair-dye composition; between about 0.1 and 50 percent by weight of anoxidizing agent comprising a hydrogen peroxide-yielding compoundselected from the group consisting of hydrogen peroxide and ureaperoxide and an aqueous carrier; and between about 25 and 75 percent byweight of a conditioning agent selected from the group consisting ofmilk and beer to the hair; and B. allowing sufficient time for colordevelopment.
 10. A method for coloring hair on a human head comprisingthe steps of: A. applying a hair-coloring mixture comprising betweenabout 25 and 75 percent by weight of an aqueous oxidative hair-dyecomposition; between about 0.1 and 50 percent by weight of an oxidizingagent comprising a hydrogen peroxide-yielding compound selected from thegroup consisting of hydrogen peroxide and urea peroxide and an aqueouscarrier containing a viscosity imparting ingredient selected from thegroup consisting of methyl cellulose, hydroxyethyl cellulose, carboxymethyl cellulose, and polyvinylpyrrolidone, and between about 25 and 75percent by weight of a conditioning agent selected from the groupconsisting of milk and beer to the hair; and B. allowing sufficient timefor color development.
 11. A method for coloring the hair on a humanhead comprising the steps of: A. applying a hair-coloring mixturecomprising between about 25 and 75 percent by weight of an aqueousoxidative hair-dye composition; and between about 25 and 75 percent byweight of an oxidizing agent selected from the group consisting of ureaperoxide and hydrogen peroxide and an aqueous carrier containing apolyhydroxy alcohol selected from the group consisting of glycerine andpropylene glycol to the hair; and B. allowing sufficient time for colordevelopment.